Allyl esters of 2-norbornane acrylic acids and 2-norbornylidene propionic aicds and perfumery uses thereof

ABSTRACT

Described are allyl esters of 2-norbornane acrylic acids and 2-norbornylidene propionic acids defined according to the generic structure: ##STR1## wherein the wavy line represents a carbon-carbon single bond or a carbon-carbon double bond; wherein one of the dashed lines is carbon-carbon single bond and the other of the dashed lines is a carbon-carbon double bond; and wherein R represents methyl or hydrogen; as well as methods for augmenting or enhancing the aroma of consumable materials including perfumes, colognes and perfumed articles.

This is a Divisional of application Ser. No. 08/450,823 filed on May 25,1995.

BACKGROUND OF THE INVENTION

The instant invention provides allyl esters of 2-norbornane acrylicacids and 2-norbornylidene propionic acids defined according to thestructure: ##STR2## wherein the wavy line represents a carbon-carbonsingle bond or a carbon-carbon double bond; and wherein one of thedashed lines is carbon-carbon single bond and the other of the dashedlines is a carbon-carbon double bond and wherein R represents methyl orhydrogen and uses thereof for augmenting, enhancing or imparting aromasin or to perfume compositions, colognes and perfumed articles (e.g.,perfumed plastics, solid or liquid anionic, cationic, nonionic orzwitterionic detergents, fabric softener compositions or dryer addedfabric softener articles).

Inexpensive compositions of matter which can provide coconut,pineapple-like, fruity, lactonic, coumarin-like, sweet, animalic andsweaty aromas with floral undertones and pineapple, coconut, galbanum,sweet, herbaceous, oolong tea-like, sweaty and animalic topnotes arehighly desirable in the art of perfumery. Many of the natural materialswhich provide such fragrances and contribute such desired nuances toperfumery compositions as well as perfumed articles including solid orliquid anionic, cationic, nonionic or zwitterionic detergents, perfumedpolymers, fabric softener compositions, fabric softener articles, hairpreparations, cosmetic powders and the like are high in cost, vary inquality from one batch to another and/or are generally subject to theusual variations of natural products.

Thus, the search for materials which can provide more refined coconut,pineapple-like, fruity, lactonic, coumarin-like, sweet, animalic andsweaty aromas has been difficult and relatively costly in the areas ofboth natural products and synthetic products.

2-Norbornyl carboxylic acid esters are known in the prior art for theiruses in perfumery. Thus, German Offenlegungsschrift 2,163,770 publishedon Jul. 5, 1973 discloses the use of compounds defined according to thestructure: ##STR3## wherein R represents C₁ -C₅ alkyl in perfumery.German Offenlegungsschrift 2,163,770 is abstracted at ChemicalAbstracts, Volume 79 (1973) 78231b.

German Offenlegungsschrift 2,517,620 published on Nov. 4, 1976 disclosesuses of the compounds having the structures: ##STR4## in perfumery.German Offenlegungsschrift 2,517,620 is abstracted at ChemicalAbstracts, Volume 86 (1977) 72035p.

Mixtures of compounds having the structures: ##STR5## as well asmixtures of compounds having the structures: ##STR6## are disclosed byKlemarczyk, et al, U.S. Pat. No. 4,319,036 issued on Mar. 9, 1982.

U.S. Pat. No. 4,728,747 issued on Mar. 1, 1988, Hoffman, et al,discloses compounds having the generic structure: ##STR7## wherein R₁represents C₁ -C₃ alkyl; R₂ represents C₁ -C₈ alkyl; R₃ and R₄, takentogether, can be the structure: ##STR8## or R₃ is hydrogen when R₄ isthe moiety: ##STR9##

The Hoffman, et al patent actually discloses the genus defined accordingto the structure: ##STR10## wherein R represents methyl or ethyl; R₁represents C₁ -C₃ alkyl; and R₂ represents C₁ -C₈ alkyl.

Although the Hoffman, et al reference does not disclose the followingcompounds, the following compounds are covered within the Hoffman genus:

(1) the compound having the structure: ##STR11## (2) the compound havingthe structure: ##STR12## (3) the compound having the structure:##STR13## (4) the compound having the structure: ##STR14##

Nothing in the prior art sets forth the allyl esters of 2-norbornaneacrylic acids and 2-norbornylidene propionic acids of our invention.Furthermore, nothing in the prior art infers that compounds such as theallyl esters of 2-norbornane acrylic acids and 2-norbornylidenepropionic acids of our invention can have the unexpected, unobvious andadvantageous perfumery properties insofar as strength, substantivity andquality of fragrance.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GC spectrum for the crude reaction product of Example I(A)containing the compound having the structure: ##STR15##

FIG. 2 is the GC spectrum for the "rushed over" distillation product ofExample I(B) containing the compound having the structure: ##STR16##

FIG. 3 is the GC spectrum for the reaction product of Example I(B)(crude reaction product).

FIG. 4 is another GC spectrum for the crude reaction product of ExampleI(B).

FIG. 5 is the NMR spectrum for the compound having the structure:##STR17## prepared according to Example I(B).

FIG. 5A is an enlargement of section "A" of the NMR spectrum of FIG. 5.

FIG. 5B is an enlargement of section "B" of the NMR spectrum of FIG. 5.

FIG. 5C is an enlargement of section "C" of the NMR spectrum of FIG. 5.

FIG. 5D is an enlargement of section "D" of the NMR spectrum of FIG. 5.

FIG. 6 is the infrared spectrum for the compound having the structure:##STR18## prepared according to Example I(B).

FIG. 7 is the GC spectrum for the reaction product of Example IIcontaining the compound having the structure: ##STR19##

FIG. 8 is the NMR spectrum for the compound having the structure:##STR20## prepared according to Example II.

FIG. 8A is an enlargement of section "A" of the NMR spectrum of FIG. 8.

FIG. 8B is an enlargement of section "B" of the NMR spectrum of FIG. 8.

FIG. 8C is an enlargement of section "C" of the NMR spectrum of FIG. 8.

FIG. 8D is an enlargement of section "D" of the NMR spectrum of FIG. 8.

FIG. 9 is the infrared spectrum for the compound a having the structure:##STR21## prepared according to Example II.

FIG. 10 is the GC spectrum for the crude reaction product of Example IIIcontaining the compound having the structure: ##STR22##

FIG. 11 is the GC spectrum for distillation Fraction 6 of thedistillation product of the reaction product of Example III containingthe compound having the structure: ##STR23##

FIG. 12 is the NMR spectrum for the compound having the structure:##STR24## prepared according to Example III.

FIG. 12A is an enlargement of section "A" of the NMR spectrum of FIG.12.

FIG. 12B is an enlargement of section "B" of the NMR spectrum of FIG.12.

FIG. 13 is the infrared spectrum for the compound having the structure:##STR25## prepared according to Example III.

FIG. 14 is the GC spectrum for Fraction 7 of the distillation product ofthe reaction product of Example IV containing the compound having thestructure: ##STR26##

FIG. 15 is the NMR spectrum for the compound having the structure:##STR27## prepared according to Example IV.

FIG. 15A is an enlargement of section "A" of the NMR spectrum of FIG.15.

FIG. 15B is an enlargement of section "B" of the NMR spectrum of FIG.15.

FIG. 15C is an enlargement of section "C" of the NMR spectrum of FIG.15.

FIG. 16 is the infrared spectrum for the compound having the structure:##STR28## prepared according to Example IV.

FIG. 17 represents a cutaway side elevation view of the apparatus usedin forming perfumed polymers which contain imbedded in the intersticesthereof at least one of the allyl esters of 2-norbornane acrylic acidsand 2-norbornylidene propionic acids of our invention.

FIG. 18 is a front view of the apparatus of FIG. 17 looking in thedirection of the arrows.

DETAILED DESCRIPTION OF THE DRAWINGS

Referring to the GC spectrum of FIG. 3, FIG. 3 is a GC spectrum of thereaction product of Example I(B). The peaks indicated by referencenumeral 33 are the peaks for isomers of the compound having thestructure: ##STR29## The peaks indicated by reference numeral 32 are forisomers defined according to the structure: ##STR30## The peaksindicated by reference numeral 31 are the peaks for a lactone impuritydefined according to the structure: ##STR31##

By the same token, the GC spectrum of FIG. 4 is also for the crudereaction product of Example I(B) run under different conditions. Thepeaks indicated by reference numeral 42 are the peaks for isomers of thedesired compound having the structure: ##STR32## The peaks indicated byreference numeral 41 are for isomers of the compound defined accordingto the structure: ##STR33## The peaks indicated by reference numeral 43are for isomers defined according to the structure: ##STR34##

Referring to FIG. 10, the GC spectrum for the crude reaction product ofExample III, the peak indicated by reference numeral 101 is the peak forthe desired product having the structure: ##STR35## The peaks indicatedby reference numeral 102 is for isomers defined according to thestructure: ##STR36##

The peaks indicated by reference numeral 103 are for the carboxylicacids defined according to the structure: ##STR37##

Referring to FIG. 11, the GC spectrum for distillation Fraction 6 of thedistillation product of the reaction product of Example III, the peakindicated by reference numeral 110 is the peak for the compound havingthe structure: ##STR38## (conditions: carbowax column programmed from80° to 220° C. at 8° C. per minute).

Referring to FIGS. 17 and 18, there is provided a process for formingscented polymer elements (wherein the polymer may be a thermoplasticpolymer such as a low density polyethylene or polypropylene orcopolymers of ethylene and vinyl acetate or mixtures of polymers andcopolymers such as copolymers of ethylene and vinyl acetate andpolyethylene) such as pellets useful in the formation of plasticparticles useful in fabricating certain articles which may be perfumed.This process comprises heating the polymer or mixture of polymers to themelting point of said polymer or mixture of polymers, e.g., 250° C. inthe case of low density polyethylene. The lower most portion of thecontainer is maintained at a slightly lower temperature and the materialin the container is taken off at such location for delivery through theconduit. Thus, referring to FIGS. 17 and 18, in particular, theapparatus used in producing such elements comprises a device for formingthe polymer containing perfume, e.g., polyethylene orpolyethylene-polyvinyl acetate or mixtures of same or polypropylene,which comprises a vat or container 212 into which the polymer takenalone or in admixture with other copolymers and the perfuming substancewhich is at least one of the allyl esters of 2-norbornane acrylic acidsand 2-norbornylidene propionic acids of our invention and othercompatible perfumes is placed. The container is closed by means of anair-tight lid 228 and clamped to the container by bolts 265. A stirrer273 traverses the lid or cover 228 in an air-tight manner and isrotatable in a suitable manner. A surrounding cyclinder having heatedcoils 212A which are supplied with electric current through cable 214from a rheostat or control 216 is operated to maintain the temperatureinside the container 212 such that the polymer in the container will bemaintained in the molten or liquid state. It has been found advantageousto employ polymers at such a temperature that the viscosity will be inthe range of 90-100 Sayboldt seconds. The heater is operated to maintainthe upper portion of the container 212 within a temperature range of,for example, 220°-270° C. in the case of low density polyethylene. Thebottom portion of the container 212 is heated by means of heating coils212A regulated through the control 220 connected thereto through aconnecting wire 222 to maintain the lower portion of the container 212within the temperature range of 220°-270° C.

Thus, the polymer or mixture of polymers added to the container 212 isheated from 10-12 hours, whereafter the perfume composition or perfumematerial which contains one or more of the allyl esters of 2-norbornaneacrylic acids and 2-norbornylidene propionic acids of our invention isquickly added to the melt. Generally, about 10-45 percent by weight ofthe resulting mixture of the perfumery substance is added to thepolymer.

After the perfume material is added to the container 212, the mixture isstirred for a few minutes, for example, 5-15 minutes and maintainedwithin the temperature ranges indicated previously by the heating coils212A. The controls 216 and 220 are connected through cables 224 and 226to a suitable supply of electric current for supplying the power forheating purposes.

Thereafter, the valve "V" is opened permitting the mass to flowoutwardly through conduit 232 having a multiplicity of orifices 234adjacent to the lower side thereof. The outer end of the conduit 232 isclosed so that the liquid polymer in intimate admixture with one or moreof the allyl esters of 2-norbornane acrylic acids and 2-norbornylidenepropionic acids of our invention or mixture of perfume substances andone or more of the allyl esters of 2-norbornane acrylic acids and2-norbornylidene propionic acids of our invention will continuously dropthrough the orifices 234 downwardly from the conduit 232. During thistime, the temperature of the polymer intimately admixed with theperfumery substance in the container 212 is accurately controlled sothat a temperature in the range of from about 240°-250° C., for example(in the case of low density polyethylene), will exist in the conduit232. The regulation of the temperature through the controls 216 and 220is essential in order to insure temperature balance to provide for thecontinuous dripping or dropping of molten polymer intimately admixedwith the perfume substance which is all of or which contains at leastone of the allyl esters of 2-norbornane acrylic acids and2-norbornylidene propionic acids of our invention, through the orifices234 at a rate which will insure the formation of droplets 236 which willfall downwardly onto a moving conveyor belt 238 caused to run betweenconveyor wheels 240 and 242 beneath the conduit 232.

When the droplets 236 fall onto the conveyor belt 238, they form pelletswhich harden almost instantaneously and fall off the end of the conveyorbelt 238 into a container 245 which is advantageously filled with wateror some other suitable cooling liquid to insure the rapid cooling ofeach of the pellets. The pellets are then collected from the container245 and utilized for the formation of other functional products, e.g.,garbage bags and the like. The conveyor belt 238 is cooled by coolingwater 254 contained in container 250 having sidewalls 248. The coolingwater is absorbed in sponge 256 which cools the conveyor belt 238 aswheels 240 and 242 are moving.

THE INVENTION

The present invention provides allyl esters of 2-norbornane acrylicacids and 2-norbornylidene propionic acids defined according to thegeneric structure: ##STR39## wherein the wavy line represents acarbon-carbon single bond or a carbon-carbon double bond; wherein one ofthe dashed lines is a carbon-carbon single bond and the other of thedashed lines is a carbon-carbon double bond; and wherein R representsmethyl or hydrogen. Preferably, the allyl esters of 2-norbornane acrylicacids and 2-norbornylidene propionic acids of our invention arecompounds having the structures: ##STR40## which include each of thegeometric and optical isomers of the compounds.

The present invention also provides processes for preparing such allylesters of 2-norbornane acrylic acids and 2-norbornylidene propionicacids by means of carrying out the reaction sequence: ##STR41## and theneither reacting the resultant reaction product with allyl alcoholaccording to the reaction: ##STR42## or first reacting the resultingproduct with an esterification reagent according to the reaction:##STR43## wherein the compound, to wit: R'! --Z is an esterificationreagent wherein R' represents C₁ -C₅ alkyl and Z represents hydroxyl,iodide or sulfate. In the latter case, the resulting alkyl ester is thenreacted with allyl alcohol according to the reaction: ##STR44##

When it is desired to make compounds such as those having the structure:##STR45## the reaction: ##STR46## is carried out in the presence of amixed pyridine and piperidine catalyst at a temperature of 90° C. At theend of the reaction forming the dicarboxylic acid, the reaction mass pHis raised using a strong base (such as 50% sodium hydroxide solution) toa range of between 11 and 11.5. In order to decarboxylate the resultingproduct, the reaction mass is acidified and heated whereby the pH isreduced to about 1 using, for example, hydrochloric acid.

When it is desired to produce compounds such as those having thestructures: ##STR47## a trialkyl amine catalyst is used for thereaction: ##STR48## which trialkyl amine is defined according to thestructure: ##STR49## wherein R₁, R₂ and R₃ are the same or different C₁-C₃ alkyl, preferably methyl or ethyl. The reaction temperature for thereaction: ##STR50## is still at about 90° C. The pH of the reaction massis raised at the end of the reaction to approximately 12 and is thenlowered to approximately 1.5 with strong acid.

The reaction: ##STR51## is carried out in the presence of an acidcatalyst such as methane sulfonic acid or an acid ion exchange resincatalyst a such as AMBERLYST® 15. The reaction is carried out at refluxconditions, preferably at atmospheric pressure at a temperature in therange of from about 150° up to about 170° C. for a period of time offrom about 10 up to about 15 hours.

At the end of the reaction, the reaction mass is "worked up" by means ofextraction followed by fractional distillation using standard fractionaldistillation techniques.

Thus, the allyl esters of 2-norbornane acrylic acids and2-norbornylidene propionic acids of our invention augment, enhance orimpart coconut, pineapple-like, fruity, lactonic, coumarin-like, sweet,animalic and sweaty aromas with floral undertones and pineapple,coconut, galbanum, sweet, herbaceous, oolong tea-like, sweaty andanimalic topnotes in or to perfume compositions, colognes and perfumedarticles (including soaps, anionic, cationic, nonionic or zwitterionicdetergents, fabric softener compositions, fabric softener articles,optical brightener compositions, perfumed polymers, hair preparationsand the like, thus fulfilling a need in the field of perfumery as wellas detergent, cologne, fabric softener and cosmetic manufacture.

Examples of the allyl esters of 2-norbornane acrylic acids and2-norbornylidene propionic acids of our invention which are useful inthe practice of our invention and their perfumery properties are setforth in the following Table I.

                  TABLE I                                                         ______________________________________                                        Structure of Compound                                                                           Perfumery Evaluation                                        ______________________________________                                        The compound having the                                                                         A coconut, pineapple-like,                                  structure:        fruity, lactonic aroma with                                  ##STR52##        pineapple and galbanum topnotes and floral undertones       prepared according to Example                                                 I(B) bulked distillation                                                      Fractions 7-20.                                                               The compound having the                                                                         A coumarin-like, lactonic                                   structure:        aroma, with sweet, herbaceous                                ##STR53##        and oolong tea-like topnotes.                               prepared according to Example                                                 II.                                                                           The compound having the                                                                         A sweaty, animalic, fruity                                  structure:        and pineapple aroma with                                     ##STR54##        galbanum, sweaty and animalic topnotes.                     prepared according to Example                                                 III, distillation Fraction 6.                                                 The compound having the                                                                         A sweaty, animalic aroma with                               structure:        coconut, sweaty, and animalic                                ##STR55##        topnotes.                                                   prepared according to Example                                                 IV, bulked distillation                                                       Fractions 5-10.                                                               ______________________________________                                    

One or more of the of the allyl esters of 2-norbornane acrylic acids and2-norbornylidene propionic acids of our invention prepared in accordancewith the process of our invention and one or more auxiliary perfumeingredients including, for example, alcohols, aldehydes, ketones,terpenic hydrocarbons, nitriles, esters other than the esters of ourinvention, lactones, natural essential oils and synthetic essential oilsmay be admixed so that the combined odors of the individual componentsproduce a pleasant and desired fragrance particularly and preferably inthe floral and galbanum area of fragrances. Such perfume compositionsusually contain (a) the main note or the "bouquet" or foundation stoneof the composition; (b) modifiers which round off and accompany the mainnote; (c) fixatives which include odorous substances which lend aparticular note to the perfume throughout all stages of evaporation andsubstances which retard evaporation; and (d) topnotes which are usuallylow boiling, fresh smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the allyl esters of 2-norbornane acrylic acids and 2-norbornylidenepropionic acids of our invention prepared in accordance with theprocesses of our invention can be used to alter, modify, impart orenhance the aroma characteristics of a perfume composition, for example,by utilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of one or more of the allyl esters of 2-norbornane acrylicacids and 2-norbornylidene propionic acids of our invention prepared inaccordance with the processes of our invention which will be effectivein perfume compositions as well as in perfumed articles (e.g., anionic,nonionic, cationic and zwitterionic solid or liquid detergents, soaps,fabric softener compositions, drier-added fabric softener articles,optical brightener compositions, perfumed polymers and textile sizingagents) and colognes depends on many factors including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 0.01% ofone or more of the allyl esters of 2-norbornane acrylic acids and2-norbornylidene propionic acids of our invention prepared in accordancewith the processes of our invention and even up to 100% of one or moreof the allyl esters of 2-norbornane acrylic acids and 2-norbornylidenepropionic acids of our invention or even less(e.g., 0.005%) can be usedto impart, augment or enhance coconut, pineapple-like, fruity, lactonic,coumarin-like, sweet, animalic and sweaty aromas with floral undertonesand pineapple, coconut, galbanum, sweet, herbaceous, oolong tea-like,sweaty and animalic topnotes in or to soaps, cosmetics, solid or liquidanionic, nonionic, cationic and zwitterionic detergents, fabric softenercompositions, fabric softener articles, optical brightener compositions,textile sizing compositions, perfumed polymers or other products. Theamount employed can range up to 100% of the fragrance components andwill depend on considerations of cost, nature of the end product, theeffect desired on the finished product and the particular fragrancesought.

One or more allyl esters of 2-norbornane acrylic acids and2-norbornylidene propionic acids prepared in accordance with theprocesses of our invention are useful (taken alone or together withother ingredients in perfume compositions) as (an) olfactorycomponent(s) in detergents and soaps, space odorants and deodorants,perfumes, colognes, toilet water, bath preparations, such as creams,deodorants, hand lotions and sun screens; powders such as talcs, dustingpowders, face powders, and perfumed polymers and articles of manufactureproduced from said perfumed polymers, e.g., garbage bags, children'stoys and the like. When used as (an) olfactory component(s) as little as0.2% of one or more of the allyl esters of 2-norbornane acrylic acidsand 2-norbornylidene propionic acids of our invention prepared inaccordance with the processes of our invention will suffice to impart,augment or enhance intense and substantive coconut, pineapple-like,fruity, lactonic, coumarin-like, sweet, animalic and sweaty aromas withfloral undertones and pineapple, coconut, galbanum, sweet, herbaceous,oolong tea-like, sweaty and animalic topnotes to floral and galbanumfragrance formulations. Generally, no more than 6% of one or more of theallyl esters of 2-norbornane acrylic acids and 2-norbornylidenepropionic acids of our invention based on the ultimate end product asrequired in the perfumed article composition is required. Accordingly,the range of allyl esters of 2-norbornane acrylic acids and2-norbornylidene propionic acids in the perfumed article is from about0.2% by weight of the allyl esters of 2-norbornane acrylic acids and2-norbornylidene propionic acids up to about 6% by weight of the allylesters of 2-norbornane acrylic acids and 2-norbornylidene propionicacids based on the total weight of the perfumed article.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle or carrier for one or more of the allylesters of 2-norbornane acrylic acids and 2-norbornylidene propionicacids of our invention prepared in accordance with the processes of ourinvention. The vehicle can be a liquid such as a non-toxic alcohol,e.g., ethyl alcohol, a non-toxic glycol, e.g., propylene glycol or thelike. The carrier can also be an absorbent solid such as gum (e.g., gumarabic or xanthan gum) or components for encapsulating the compositions(such as gelatin as by coacervation) or such as a urea formaldehydeprepolymer forming a capsule shell around a liquid perfumed center.

Our invention also relates to the utilization of controlled releasedtechnology for the controlled release of perfumes into gaseousenvironments from polymers such as mixtures of epsilon polycaprolactonepolymers and polyethylene which polyepsilon caprolactone polymers aredefined as set forth at columns 29-30 of U.S. Pat. No. 4,521,634 issuedon Jun. 4, 1985, the specification for which is incorporated byreference herein.

The following Examples I-IV serve to illustrate processes for preparingthe allyl esters of 2-norbornane acrylic acids and 2-norbornylidenepropionic acids of our invention. The examples following Example IV areillustrative of the organoleptic utilities of the allyl esters of2-norbornane acrylic acids and 2-norbornylidene propionic acids of ourinvention. All parts and percentages given herein are by weight unlessotherwise specified.

EXAMPLE I Preparation of the Allyl Ester of 2-Norbornane Acrylic Acid

Example I(A): Preparation from the Methyl Ester of 2-Norbornane AcrylicAcid

Reaction: ##STR56##

54 Grams of methyl-2-norbornane acrylate having the structure: ##STR57##32 grams of allyl alcohol, 75 grams of cumene and 1.5 grams of sodiumcarbonate were charged to a 250 ml distillation flask equipped withheating mantle, thermometer and reflux condenser. The reaction mass isrefluxed for a period of 2 hours at approximately 165° C.

The reaction mass is then washed with two 200 ml portions of water. Theresulting product having the structure: ##STR58## was then trapped outfor odor using a ten foot×half inch 10% SE-30 stainless steel columnprogrammed from 75°-220° C. at 50° C. per minute. The GC spectrum forthe compound having the structure: ##STR59## prepared in this manner isset forth in FIG. 1. Example I(B): Product Prepared Using 2-NorbornaneAcrylic Acid Reactant

Reactions: ##STR60##

Into a 5 liter reaction flask equipped with stirrer, thermometer, refluxcondenser and heating mantle are placed 875 grams of norbornanecarboxaldehyde having the structure: ##STR61## 930 grams of malonic acidhaving the structure: ##STR62## 1,000 grams of pyridine and 5.0 grams ofpiperidine. With stirring, the reaction mass is heated to 90° C. andmaintained at 90° C. for a period of 10.5 hours. The reaction mass isthen slowly cooled to a temperature of between 30° and 35° C. and 343.2grams of 50% sodium hydroxide (aqueous) is added to the reaction massbringing the reaction mass pH to 11.2.

The pyridine was stripped off at 32 mm/Hg. pressure at 50° C., removing934 grams of pyridine.

1,300 Grams of hydrochloric acid (concentrated) was added to thereaction mass bringing the reaction mass pH to approximately 0.09.

The 1,300 grams of hydrochloric acid caused dissolution of all solids inthe reaction mass.

The reaction mass exists now in two phases: an aqueous phase and anorganic phase. The aqueous phase was extracted with 200 grams of toluenethree times. The toluene layer and the toluene extracts were againwashed with three 200 gram portions of 10% aqueous hydrochloric acid.The toluene layer is then returned to the 5 liter reaction vessel and400 grams of allyl alcohol and 7.5 grams of methane sulfonic acid isadded using a Bidwell trap. The reaction mass is refluxed for a periodof 11 hours removing water using the Bidwell trap. An additional 100grams of allyl alcohol is then added and the reaction mass is refluxedfor a period of 7 hours. Then another 100 grams of allyl alcohol isadded and the reaction mass is refluxed for an additional 7 hours.

7.5 Grams of sodium acetate is added to the reaction mass and thereaction mass is stirred for a period of 30 minutes. The allyl alcohol(excess) is then stripped off and the resulting product is washed withtwo 200 grams of water bringing the pH of the reaction product to 5.

167.5 Grams of crude reaction mass is recovered containing the compoundhaving the structure: ##STR63##

The resulting product is first rushed over on a 12 inch Vigreux columnand then fractionally distilled through an 8 inch Goodloe packed columnyielding the following fractions:

    ______________________________________                                               Vapor     Liquid                                                       Fraction                                                                             Temperature                                                                             Temperature                                                                             Vacuum mm/Hg.                                                                           Weight of                                Number (°C.)                                                                            (°C.)                                                                            Pressure  Fraction                                 ______________________________________                                        1      79/83      23/119   1.7/1.1   11.6                                     2      91        122       1.6       10.8                                     3      93        123       1.6       20.6                                     4      93        122       1.6       20.0                                     5      94        122       1.6       23.2                                     6      93        122       1.5       42.6                                     7      93        123       1.5       57.8                                     8      93        123       1.5       39.8                                     9      93        122       1.5       43.2                                     10     94        125       1.5       41.3                                     11     94        127       1.5       57.2                                     12     95        128       1.5       46.2                                     13     95        128       1.5       55.1                                     14     105       130       1.8       43.7                                     15     101       130       2.0       93.4                                     16     54/96     120/128   1.5       27.4                                     17     95        127       1.5       49.5                                     18     95        127       1.5       51.2                                     19     95        125       1.4       88.9                                     20     96        126       1.4       115.6                                    21     96        127       1.4       82.3                                     22     96        126       1.4       87.8                                     23     96        134       1.5       39.6                                     24     78        160       1.6       20.6                                     25     39        185       1.6       6.9                                      ______________________________________                                    

Fractions 7-20 are bulked. Bulked distillation Fractions 7-20 have GCspectra as set forth in FIGS. 3 and 4.

The conditions for the GC spectrum for FIG. 3 are: 50 meter×0.32 mmbonded fused silica column coated with methyl silicone programmed from75°-225° C. at 2° C. per minute.

The conditions for the GC spectrum for FIG. 4 are: carbowax 20M coatedon non-bonded fused silica, the column having measurements of 50meters×0.32 mm programmed from 75°-225° C. at 2.0° C. per minute.

EXAMPLE II Preparation of 2-(5-Methylbnorbornyl) Acrylic Acid, AllylEster

Reaction: ##STR64##

Into a 100 cc reaction vessel equipped with stirrer, thermometer andreflux condenser are placed 10 grams of the compound having thestructure: ##STR65## 20 grams of allyl alcohol; and 2.0 grams AMBERLYST®15 acid ion exchange catalyst.

The reaction mass is heated to reflux at 95°-96° C. and maintained at95°-96° C. with stirring during reflux for a period of 17 hours. Theresulting product is trapped on a GC apparatus (gas chromatographapparatus) with the GC column being programmed from 80°-220° C. at 8° C.per minute (SE megabor column). The GC spectrum is set forth in FIG. 7.

The above reaction is repeated on a large scale yielding the compoundhaving the structure: ##STR66## in a large enough quantity to prepare afragrance formulation as set forth in Example V, infra.

EXAMPLE III Preparation of the Allyl Ester of 2-Norbornylidene AcrylicAcid

Reactions: ##STR67##

Into a 2 liter reaction flask equipped with stirrer, thermometer andreflux condenser are placed 275 grams of 5-norbornane-2-carboxaldehydehaving the structure: ##STR68## 312 grams of malonic acid having thestructure: ##STR69## 700 grams of triethyl amine. With stirring, thereaction mass heated to 90° C. and maintained at 90° C. for a period of15.5 hours.

At the end of the 15.5 hour period, the reaction mass is cooled to27°-30° C. and 750 grams of a 50% sodium hydroxide solution is added tothe reaction mass causing the pH of the reaction mass to be atapproximately 12.

300 Grams of water is then added to the reaction mass.

The reaction mass is stripped of solvent at 50° C. and 50 mm/Hg.pressure. 852 Grams of distillate are removed. The remaning product isthen acidified using 622 grams of concentrated hydrochloric acid to a pHof 1.5.

The resulting reaction mass now exists in two phases: an organic phaseand an aqueous phase.

170 Grams of the resulting carboxylic acid is admixed with 170 grams ofallyl alcohol. The resulting mixture is then heated with stirring to160° C. and maintained at 160° C. for a period of 11 hours.

At the end of the 11 hour period, the reaction product is filtered anddistilled yielding the following fractions:

    ______________________________________                                               Vapor     Liquid                                                       Fraction                                                                             Temperature                                                                             Temperature                                                                             Vacuum mm/Hg.                                                                           Weight of                                Number (°C.)                                                                            (°C.)                                                                            Pressure  Fraction                                 ______________________________________                                        1      64/88     128/129   1.6/1.6   13.6                                     2      96        130       2.4       12.0                                     3      97        130       2.4       13.5                                     4      98        131       2.4       13.1                                     5      99        130       2.4       13.3                                     6      100       131       2.4       13.1                                     7      77        128       0.8       13.5                                     8      77        128       0.8       10.3                                     9      77        130       0.8       8.3                                      10     77        139       0.8       9.6                                      11     80        156       0.9       4.3                                      12     --        200       1.1       6.6                                      ______________________________________                                    

It should be noted that the peaks on the GC spectrum of FIG. 10indicated by reference numeral 102 are for isomers of a lactone havingthe structure: ##STR70## with the desired products peak indicated byreference numeral 101 (having the structure: ##STR71##

The amount of lactone having the structure: ##STR72## can be diminishedif instead of carrying out the reaction: ##STR73## the reaction:##STR74## is carried out whereby the carboxylic acid having thestructure: ##STR75## is first esterified as with dimethyl sulfate,methyl alcohol (in the presence of a sulfuric acid catalyst or methyliodide).

EXAMPLE IV Production of 2-Dehydronorbornylidene Propionic Acid, AllylEster

Reactions: ##STR76##

Into a 2 liter reaction vessel equipped with stirrer, thermometer andreflux condenser are placed 200 grams of 5-norbornene-2-carboxaldehydehaving the structure: ##STR77## 250 grams of malonic acid having thestructure: ##STR78## 560 grams of triethyl amine. With stirring, thereaction mass is heated to 88° C. and maintained at 88° C. (refluxconditions) for a period of 17 hours.

At the end of the 17 hour period, the reaction mass is cooled to 32°-35°C.

A 10% aqueous sodium hydroxide solution is then added to the reactionmass (640 grams) causing the reaction mass pH to be at 9. An additional20% aqueous sodium hydroxide mixture (120 grams) is then added to thereaction mass to bring the reaction mass to a pH of 12.

The triethyl amine catalyst is then stripped from the reaction mass at100 mm/Hg. until 660 grams of distillate was removed.

The remainder of the reaction mass is then extracted with three 150 gramportions of toluene and then acidified using 316 grams of concentratedhydrochloric acid.

The reaction mass now exists in two phases: an organic phase and anaqueous phase. The organic phase is the lower phase weighing 350 grams.The upper phase is the acid phase weighing 1,429 grams.

The organic phase is admixed with 150 grams of allyl alcohol and theresulting mixture is heated to 160° C. and maintained at 160° C. for aperiod of 7 hours. NMR, IR and mass spectral analysis yield theinformation that the resulting product has the structure: ##STR79##

The resulting product is distilled on a ten-plate Vigreux columnyielding the following fractions:

    ______________________________________                                               Vapor     Liquid                                                       Fraction                                                                             Temperature                                                                             Temperature                                                                             Vacuum mm/Hg.                                                                           Weight of                                Number (°C.)                                                                            (°C.)                                                                            Pressure  Fraction                                 ______________________________________                                        1      25/91     125/130   1.4       4.5                                      2      89        120       1.2       5.6                                      3      87        119       1.1       9.6                                      4      83        120       0.8       10.8                                     5      83        121       0.8       13.6                                     6      83        123       0.8       8.6                                      7      83        118       0.8       13.0                                     8      83        118       0.8       15.5                                     9      83        115       0.7       15.5                                     10     75        154       0.7       8.1                                      11     88        200       0.7       3.3                                      ______________________________________                                    

EXAMPLE V Preparation of Floral Fragrance

The following mixture is prepared:

    ______________________________________                                        Ingredients       V(A)   V(B)    V(C) V(D)                                    ______________________________________                                        Hydroxcitronellal 22%    22%     22%  22%                                     Phenyl Ethyl Alcohol                                                                            12%    12%     12%  12%                                     Heliotropine      12%    12%     12%  12%                                     Linalool          8%     8%      8%   8%                                      Cinnamic Alcohol  4%     4%      4%   4%                                      Indole (10% in Diethyl Phthalate)                                                               2%     2%      2%   2%                                      Benzyl Acetate    8%     8%      8%   8%                                      Anisic Alcohol    8%     8%      8%   8%                                      Coumarin (10% in Diethyl Phthalate)                                                             4%     4%      4%   4%                                      The compound having the structure:                                                              4%     0%      0%   0%                                       ##STR80##                                                                    (prepared according to Example I(B)                                           bulked distillation Fractions 7-20).                                          The compound having the structure:                                                              0%     4%      0%   0%                                       ##STR81##                                                                    prepared according to Example II.                                             The compound having the structure:                                                              0%     0%      4%   0%                                       ##STR82##                                                                    prepared according to Example III                                             distillation Fraction 6.                                                      The compound having the structure:                                                              0%     0%      0%   4%                                       ##STR83##                                                                    prepared according to Example IV                                              bulked distillation Fractions 5-10.                                           ______________________________________                                    

When the compound having the structure: ##STR84## is added to thisfloral fragrance, the floral fragrance achieves coconut, pineapple-like,fruity and lactonic undertones with pineapple and galbanum topnotes.Accordingly, the fragrance of Example V(A) can be described as:

"A floral aroma with coconut, pineapple-like, fruity and lactonicundertones and pineapple and galbanum topnotes."

When the compound having the structure: ##STR85## is added to thisfloral fragrance, the floral fragrance gains coumarin-like and lactonicundertones with sweet, herbaceous and oolong tea-like topnotes.Accordingly, the fragrance of Example V(B) can be described as:

"A floral aroma with coumarin-like and lactonic undertones and sweet,herbaceous and oolong tea-like topnotes."

When the compound having the structure: ##STR86## is added to thisfloral fragrance, the floral fragrance attains sweet, animalic, fruityand pineapple undertones with galbanum, sweaty and animalic topnotes.Accordingly, the fragrance of Example V(C) can be described as:

"A floral aroma with sweaty, animalic, fruity and pineapple undertonesand galbanum, sweaty and animalic topnotes."

When the compound having the structure: ##STR87## is added to thisfloral fragrance formulation, the floral fragrance formulation gainssweaty and animalic undertones and coconut, sweaty and animalictopnotes. Accordingly, the fragrance of Example V(D) can be describedas:

"A floral aroma having sweaty and animalic undertones and coconut,sweaty and animalic topnotes."

EXAMPLE VI Preparation of Cosmetic Powder Compositions

Cosmetic powder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table II below. Each of the cosmetic powder compositions has anexcellent aroma as described in Table II below:

                  TABLE II                                                        ______________________________________                                        Substance         Aroma Description                                           ______________________________________                                        The compound having the                                                                         A coconut, pineapple-like,                                  structure:        fruity and lactonic aroma with                               ##STR88##        pineapple and galbanum topnotes and floral undertones.      prepared according to Example                                                 I(B) bulked distillation                                                      Fractions 7-20.                                                               The compound having the                                                                         A coumarin-like, lactonic                                   structure:        aroma with sweet, herbaceous                                 ##STR89##        and oolong tea-like topnotes.                               prepared according to Example                                                 II.                                                                           The compound having the                                                                         A sweaty, animalic, fruity and                              structure:        pineapple aroma with galbanum,                               ##STR90##        sweaty and animalic topnotes.                               prepared according to Example                                                 III distillation Fraction 6.                                                  The compound having the                                                                         A sweaty, animalic aroma with                               structure:        coconut, sweaty and animalic                                 ##STR91##        topnotes.                                                   prepared according to Example                                                 IV bulked distillation                                                        Fractions 5-10.                                                               Perfume composition of                                                                          A floral aroma with coconut,                                Example V(A).     pineapple-like, fruity and                                                    lactonic undertones and                                                       pineapple and galbanum                                                        topnotes.                                                   Perfume composition of                                                                          A floral aroma with coumarin-                               Example V(B)      like and lactonic undertones                                                  and sweet, herbaceous and                                                     oolong tea-like topnotes.                                   Perfume composition of                                                                          A floral aroma with sweaty,                                 Example V(C).     animalic, fruity and pineapple                                                undertones and galbanum,                                                      sweaty and animalic topnotes.                               Perfume composition of                                                                          A floral aroma having sweaty                                Example V(D).     and animalic undertones and                                                   coconut, sweaty and animalic                                                  topnotes.                                                   ______________________________________                                    

EXAMPLE VII Perfumed Liquid Detergent

Concentrated liquid detergents with aromas as set forth in Table II ofExample VI (which detergents are prepared from Lysine sale of n-dodecylbenzene sulfonic acid as more specifically described in U.S. Pat. No.3,948,818 issued on Apr. 6, 1976 the specification for which isincorporated by reference herein) are prepared containing each of thesubstances set forth in Table II of Example VI, supra. They are preparedby adding and homogeneously mixing the appropriate quantity of perfumerysubstance as set forth in Table II of Example VI in the liquiddetergent. The detergents all possess aromas as set forth in Table II ofExample VI, the intensity increasing with greater concentrations ofperfumery substance of Table II of Example VI, supra.

EXAMPLE VIII Preparation of a Cologne and Handkerchief Perfume

The perfume substances of Table II of Example VI, supra, areincorporated into colognes at concentrations of 1.5%, 2.0%, 2.5%, 3.0%and 4.0% in 80%, 85% and 90% aqueous ethanols; and into a handkerchiefperfume composition at concentrations of 10%, 15%, 20%, 25% and 30% (in85%, 90% and 95% aqueous ethanols. Distinct and definitive aromas as setforth in Table II of Example VI are imparted to the cologne and to thehandkerchief perfume compositions.

EXAMPLE IX Preparation of a Detergent Composition

A total of 100 grams of a detergent powder (a nonionic detergent powdercontaining a proteolytic enzyme prepared according to Example I ofCanadian Letters Patent No. 985,190 issued on Mar. 9, 1976 thedisclosure of which is incorporated by reference herein) is mixed with0.15 grams of each of the substances set forth in Table II of ExampleVI, supra, until substantially homogeneous compositions are obtained.These compositions have excellent aromas as set forth in Table II ofExample VI.

EXAMPLE X Preparation of Soap

Each of the perfumery substances of Table II of Example VI areincorporated into soap (LVU-1) at 0.1% by weight of each substance.After two weeks in the oven at 90° F., each of the soaps showed novisual effect from the heat. Each of the soaps manifested an excellentaroma as set forth in Table II of Example VI, supra.

EXAMPLE XI Preparation of Soap Composition

100 Grams of soap chips (IVORY®, Registered Trademark of the Procter &Gamble Company of Cincinnati, Ohio) are mixed individually with one grameach of the perfumery substances of Table II of Example VI, supra, untila homogeneous composition is obtained. The homogeneous composition isthen treated under 3 atmospheres pressure at 180° C. for a period of 3hours and the resulting liquid is placed into a soap mold. The resultingsoap cakes, on cooling, manifest excellent aromas as set forth in TableII of Example VI, supra.

EXAMPLE XII Preparation of a Solid Detergent Composition

A detergent is prepared from the following ingredients according toExample I of Canadian Letters Patent No. 1,007,948 (the specificationfor which is incorporated by reference herein):

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        "Neodol 45-11" (a C.sub.14 --C.sub.15                                                             12                                                        alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                   Sodium carbonate    55                                                        Sodium citrate      20                                                        Sodium sulfate, water brighteners                                                                 q.s.                                                      ______________________________________                                    

This detergent is a "phosphate-free" detergent. A total of 100 grams ofthis detergent is admixed separately with 0.15 grams of each of theperfume substances of Table II of Example VI, supra. The detergentsamples each have excellent aromas as set forth in Table II of ExampleVI, supra.

EXAMPLE XIII

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the specification for which is incorporated by referenceherein), a non-woven cloth substrate useful as a dryer-added fabricsoftening article of manufacture is prepared, wherein the substrate, thesubstrate coating and the outer coating and the perfuming material areas follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.);

57% C₂₀₋₂₂ HAPS;

22% isopropyl alcohol;

20% antistatic agent; and

1% of one of the perfume substances of Table II of Example VI, supra.

A fabric softening composition prepared as set forth above having theabove aroma characteristics as set forth in Table II of Example VI,supra, essentially consists of a substrate having a weight of about 3grams per 100 square inches, a substrate coating of about 1.85 grams per100 square inches of substrate and an outer coating of about 1.4 gramsper 100 square inches of substrate, thereby providing a total aromatizedsubstrate and outer coating weight ratio of about 1:1 by weight ofsubstrate. The aroma set forth in Table II of Example VI is imparted ina pleasant manner to the headspace in the dryer on operation thereof,using said dryer-added fabric softening non-woven fabric.

EXAMPLE XIV Preparation of Soap Composition

100 Grams of soap chips (IVORY®, Registered Trademark of the Procter &Gamble Company of Cincinnati, Ohio) are mixed with 2 grams of a 50:50mixture of the compound having the structure: ##STR92## preparedaccording to Example I(A) and the compound having the structure:##STR93## prepared according to Example IV until a homogeneouscomposition is obtained. The homogeneous composition is then treatedunder 3 atmospheres pressure at 180° C. for a period of 3 hours and theresulting liquid is placed into a soap mold. The resulting soap cakes oncooling manifest an aroma which can be described as "coconut,pineapple-like, fruity, lactonic, sweaty and animalic with pineapple,galbanum, coconut, sweaty and animalic topnotes and floral undertones".

What is claimed is:
 1. A process for preparing an allyl ester definedaccording to the structure: ##STR94## wherein the wavy line represents acarbon-carbon single bond or a carbon-carbon double bond; and wherein Rrepresents methyl or hydrogen, comprising the steps of:(i) reactingmalonic acid having the structure: ##STR95## with the aldehyde havingthe structure: ##STR96## in the presence of the catalyst having thestructure: ##STR97## wherein R₁, R₂ and R₃ are the same or different C₁-C₃ alkyl at a temperature of 90° C. in accordance with the reaction:##STR98## whereby the compound having the structure: ##STR99## (ii) thendecarboxylating the resulting compound having the structure: ##STR100##to form the compound having the structure: ##STR101## by raising the pHof the reaction mass to approximately 12 and then lowering it toapproximately 1.5; and (iii) then esterifying the resultant compoundhaving the structure: ##STR102## by means of either: (a) reacting thecompound having the structure: ##STR103## with allyl alcohol accordingto the reaction: ##STR104## in the presence of an acid catalyst selectedfrom the group consisting of methane sulfonic acid and an acid ionexchange resin catalyst at atmospheric pressure at a temperature in therange of from about 150° C. up to about 170° C. for a period of time offrom about 10 hours up to about 15 hours; or (b) reacting the compoundhaving the structure: ##STR105## with the esterification reagent havingthe formula:

     R'!--Z

wherein R' is C₁ -C₅ alkyl and Z is selected from the group consistingof hydroxyl, iodide and sulfate according to the reaction: ##STR106##whereby the compound having the structure: ##STR107## is formed; andthen reacting the resulting compound having the structure: ##STR108##with allyl alcohol according to the reaction: ##STR109##
 2. A processfor preparing an allyl ester defined according to the structure:##STR110## wherein the wavy line represents a carbon-carbon single bondor a carbon-carbon double bond; and wherein R represents methyl orhydrogen, comprising the steps of:(i) reacting malonic acid having thestructure: ##STR111## with the aldehyde having the structure: ##STR112##in the presence of a mixed pyridine and piperidine catalyst at atemperature of 90° C. in accordance with the reaction: ##STR113##whereby the compound having the structure: ##STR114## (ii) thendecarboxylating the resulting compound having the structure: ##STR115##to form the compound having the structure: ##STR116## by raising the pHof the reaction mass to a range of from 11 up to 11.5 and then reducingthe pH of the reaction mass to a pH of about 1 while heating thereaction mass; and (iii) then esterifying the resultant compound havingthe structure: ##STR117## by means of either: (a) reacting the compoundhaving the structure: ##STR118## with allyl alcohol according to thereaction: ##STR119## in the presence of an acid catalyst selected fromthe group consisting of methane sulfonic acid and an acid ion exchangeresin catalyst at atmospheric pressure at a temperature in the range offrom about 150° C. up to about 170° C. for a period of time of fromabout 10 hours up to about 15 hours; or(b) reacting the compound havingthe structure: ##STR120## with the esterification reagent having theformula:

     R'!--Z

wherein R' is C₁ -C₅ alkyl and Z is selected from the group consistingof hydroxyl, iodide and sulfate according to the reaction: ##STR121##whereby the compound having the structure: ##STR122## is formed; andthen reacting the resulting compound having the structure: ##STR123##with allyl alcohol according to the reaction: ##STR124##